skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Modification of an ultrathin C 60 interlayer on the electronic structure and molecular packing of C8-BTBT on HOPG
X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), atomic force microscopy (AFM) and X-ray diffraction (XRD) were applied to investigate the electronic structure and molecular packing of C8-BTBT on HOPG with an ultrathin C 60 interlayer. It was found that C8-BTBT displays a Vollmer–Weber (V–W) growth mode on HOPG, with an ultrathin C 60 interlayer (0.7 nm). Compared to the uniform lying-down growth mode as directly grown on HOPG, the C8-BTBT molecules here adopt a lying-down orientation at low coverage with some small tilt angles because the π–π interaction between C8-BTBT and HOPG is partly disturbed by the C 60 interlayer, delivering a higher highest occupied molecular orbital (HOMO) in C8-BTBT. An interface dipole of 0.14 eV is observed due to electron transport from C8-BTBT to C 60 . The upward and downward band bending in C8-BTBT and C 60 , respectively, near the C8-BTBT/C 60 interface reduces the hole transport barrier at the interface, facilitating the hole injection from C 60 to C8-BTBT, while a large electron transfer barrier from C 60 to C8-BTBT is detected at this interface, which effectively limits electron injection from C 60 to C8-BTBT. The HOMO of C8-BTBT near the interface is largely lifted up by the C 60 insertion layer, which causes a p-doping effect and increases the hole mobility in C8-BTBT. Furthermore, owing to the lowest occupied molecular orbital (LUMO) of C 60 residing in the gap of C8-BTBT, charge transfer occurs between C 60 and the trap states in C8-BTBT to effectively passivate the trapping states. Our efforts aid a better understanding of the electron structure and film growth of anisotropic molecules and provide a useful strategy to improve the performance of C8-BTBT-based devices.  more » « less
Award ID(s):
1903962
PAR ID:
10227569
Author(s) / Creator(s):
; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Physical Chemistry Chemical Physics
Volume:
22
Issue:
43
ISSN:
1463-9076
Page Range / eLocation ID:
25264 to 25271
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. null (Ed.)
    Abstract Bonding in the ground state of C $${}_{2}$$ 2 is still a matter of controversy, as reasonable arguments may be made for a dicarbon bond order of $$2$$ 2 , $$3$$ 3 , or $$4$$ 4 . Here we report on photoelectron spectra of the C $${}_{2}^{-}$$ 2 − anion, measured at a range of wavelengths using a high-resolution photoelectron imaging spectrometer, which reveal both the ground $${X}^{1}{\Sigma}_{\mathrm{g}}^{+}$$ X 1 Σ g + and first-excited $${a}^{3}{\Pi}_{{\mathrm{u}}}$$ a 3 Π u electronic states. These measurements yield electron angular anisotropies that identify the character of two orbitals: the diffuse detachment orbital of the anion and the highest occupied molecular orbital of the neutral. This work indicates that electron detachment occurs from predominantly $$s$$ s -like ( $$3{\sigma}_{\mathrm{g}}$$ 3 σ g ) and $$p$$ p -like ( $$1{\pi }_{{\mathrm{u}}}$$ 1 π u ) orbitals, respectively, which is inconsistent with the predictions required for the high bond-order models of strongly $$sp$$ s p -mixed orbitals. This result suggests that the dominant contribution to the dicarbon bonding involves a double-bonded configuration, with 2 $$\pi$$ π bonds and no accompanying $$\sigma$$ σ bond. 
    more » « less
  2. Internal photoemission or hot-electron injection (HEJ) occurring at the metal-semiconductor (MS) Schottky interface has shown great promise in sub-bandgap photodetection and photovoltaics. In this paper, we put forward a plasmonic metagrating-interlayer-semiconductor (PMIS) structure that can significantly enhance the photon-to-electron conversion efficiency of HEJ-based optoelectronic devices. Thanks to the effect of image force-induced barrier lowering, a metal-interlayer-semiconductor (MIS) heterojunction with an ultrathin 2D material interlayer can considerably facilitate the hot electron transport across the Schottky barrier, resulting in a high internal quantum efficiency (IQE). Meanwhile, nanopatterning the MIS heterojunction into the plasmonic metagrating enables high optical absorption such that the device’s external quantum efficiency (EQE) can be nearly equal to its IQE. In addition, this device can be wavelength- and polarization-selective by tailoring the geometry and dimensions of plasmonic metagrating, thereby paving a promising path toward bandgap-independent photodetection, energy harvesting, and photocatalysis. 
    more » « less
  3. Here, we synthesized and characterized a novel two-dimensional (2D) conjugated electron donor–acceptor (D-A) copolymer (PBDB-T-Ge), wherein the substituent of triethyl germanium was added to the electron donor unit of the polymer. The Turbo–Grignard reaction was used to implement the group IV element into the polymer, resulting in a yield of 86%. This corresponding polymer, PBDB-T-Ge, exhibited a down-shift in the highest occupied molecular orbital (HOMO) level to −5.45 eV while the lowest unoccupied molecular orbital (LUMO) level was −3.64 eV. The peaks in UV-Vis absorption and the PL emission of PBDB-T-Ge were observed at 484 nm and 615 nm, respectively. 
    more » « less
  4. In order to shed light on metal-dependent mechanisms for O–O bond cleavage, and its microscopic reverse, we compare herein the electronic and geometric structures of O2-derived binuclear Co(III)– and Mn(III)–peroxo compounds. Binuclear metal peroxo complexes are proposed to form as intermediates during Mn-promoted photosynthetic H2O oxidation, as well as a Co-containing artificial leaf inspired by nature’s photosynthetic H2O oxidation catalyst. Crystallographic characterization of an extremely activated peroxo is made possible by working with substitution-inert, low-spin Co(III). Density functional theory (DFT) calculations show that the frontier orbitals of the Co(III)–peroxo compound differ noticeably from the analogous Mn(III)–peroxo compound. The highest occupied molecular orbital (HOMO) associated with the Co(III)–peroxo is more localized on the peroxo in an antibonding π*(O–O) orbital, whereas the HOMO of the structurally analogous Mn(III)–peroxo is delocalized over both the metal d-orbitals and peroxo π*(O–O) orbital. With low-spin d6 Co(III), filled t2g orbitals prevent π-back-donation from the doubly occupied antibonding π*(O–O) orbital onto the metal ion. This is not the case with high-spin d4 Mn(III), since these orbitals are half-filled. This weakens the peroxo O–O bond of the former relative to the latter. 
    more » « less
  5. The synthesis, characterization, and incorporation of open-cage [60]fullerene derivatives as electron-transporting materials (ETMs) in perovskite solar cells (PSCs) with an inverted planar (p-i-n) structure is reported. Following optical and electrochemical characterization of the open-cage fullerenes 2a–c, p-i-n PSCs with a indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene)-polystyrene sulfonate (PEDOT:PSS)/perovskite/fullerene/Ag structure were prepared. The devices obtained from 2a–b exhibit competitive power conversion efficiencies (PCEs) and improved open-circuit voltage (Voc) values (>1.0 V) in comparison to a reference cell based on phenyl-C61-butyric-acid methyl-ester (PC61BM). These results are rationalized in terms of a) the higher passivation ability of the open-cage fullerenes with respect to the other fullerenes, and b) a good overlap between the highest occupied molecular orbital/lowest unoccupied molecular orbital (HOMO/LUMO) levels of 2a–b and the conduction band of the perovskite. 
    more » « less